A mechanically interlocking epoxy resin polymer and its preparation method and application

Abstract

The present invention provides a mechanically interlocking epoxy resin polymer, a preparation method, and an application thereof. The raw materials for preparing the mechanically interlocking epoxy resin polymer include pillar aromatic hydrocarbon daisy chain polyurethane, epoxy resin, and a crosslinking agent. In the present invention, the pillar aromatic hydrocarbon daisy chain polyurethane, epoxy resin, and crosslinking agent are ring-opening polymerized to form a mechanically interlocking polymer containing a daisy chain. The crosslinking agent crosslinks the polymer containing the daisy chain into a network. The prepared mechanically interlocking epoxy resin polymer has dynamic properties, which mainly come from the host-guest recognition effect of the pillar aromatic hydrocarbon and triazole. This dynamic property can improve the mechanical properties and energy dissipation of traditional epoxy resins, allowing the epoxy resin to withstand greater stress, enhancing its toughness, and promoting maximum elongation and ductility without sacrificing the mechanical strength of the polymer.

Description

Technical Field

[0001] The present invention belongs to the technical field of epoxy resin materials, and relates to a mechanically interlocking epoxy resin polymer and a preparation method and application thereof, and specifically relates to a high-strength and high-toughness mechanically interlocking epoxy resin polymer and a preparation method and application thereof. Background Art

[0002] Epoxy resin is a thermosetting resin with advantages such as easy polymerization and processing, low curing shrinkage, and low synthetic tolerance. It is widely used as a coating and adhesive in various fields, including shipbuilding and microelectronics manufacturing. It also serves as a matrix for many different composite materials. However, the high crosslink density of epoxy resin polymers leads to high brittleness, poor toughness, and low elongation at break (<5%), which limits its application in many fields. Therefore, research on epoxy resins with high strength and toughness has attracted great attention.

[0003] Although various methods for toughening and modifying epoxy resins have been developed both domestically and internationally, such as toughening with rubber elastomers, thermoplastic resins, hyperbranched polymers, and thermotropic liquid crystal polymers, these methods still have corresponding drawbacks. For example, the incorporation of rubber elastomers can significantly reduce the epoxy resin's fracture strength and Young's modulus; the incorporation of thermoplastic resins can significantly increase the epoxy resin's viscosity, making it difficult to process; and while hyperbranched polymers and thermotropic liquid crystal polymers can achieve toughening without affecting other properties, they are difficult to synthesize and obtain.

[0004] Therefore, in the art, it is desired to develop a high-strength and high-toughness epoxy resin. Summary of the Invention

[0005] In view of the deficiencies in the prior art, the present invention aims to provide a mechanically interlocking epoxy resin polymer and a preparation method and application thereof, and specifically to provide a high-strength and high-toughness mechanically interlocking epoxy resin polymer and a preparation method and application thereof.

[0006] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides a mechanically interlocking epoxy resin polymer, wherein raw materials for preparing the mechanically interlocking epoxy resin polymer include pillar aromatic hydrocarbon daisy chain polyurethane, epoxy resin and a crosslinking agent.

[0008] In the present invention, epoxy resin, crosslinking agent, and pillar aromatic hydrocarbon daisy chain polyurethane are subjected to ring-opening polymerization to form a mechanically interlocked polymer containing a daisy chain. The crosslinking agent crosslinks the supramolecular polymer containing the daisy chain into a network. The prepared mechanically interlocked epoxy resin polymer has dynamic properties, which mainly come from the host-guest recognition effect between pillar aromatic hydrocarbons and triazoles. It can improve the mechanical properties and energy dissipation of traditional epoxy resins, enable the epoxy resin to withstand greater stress, enhance its toughness, and promote maximum elongation and ductility without sacrificing the mechanical strength of the polymer.

[0009] Preferably, the pillar aromatic daisy chain polyurethane is prepared by the following method:

[0010] Polytetrahydrofuran, a chain extender, a second cross-linking agent, an isocyanate, a catalyst and a methyl pillar[5]arene daisy chain (MeP5C10-BzOH) are added to an organic solvent and reacted to obtain the white transparent pillararene daisy chain polyurethane.

[0011] Preferably, the methyl pillar[5]arene daisy chain (MeP5C10-BzOH) is prepared by the following method:

[0012] (1) p-Dimethoxybenzene, 4-(10-bromodecanyloxy)anisole and an organic solvent are mixed, and then paraformaldehyde and boron trifluoride ether are added, reacted, and post-treated to obtain monobromosubstituted methyl pillar[5]arene (MeP5C10-Br);

[0013] (2) Mixing monobromo-substituted methyl pillar[5]arene (MeP5C10-Br), sodium azide and an organic solvent, reacting, and post-treating to obtain monoazido-substituted methoxy pillar[5]arene (MeP5C10-N3);

[0014] (3) Mixing the monoazido-substituted methoxyl pillar[5]arene (MeP5C10-N3), a capping agent, a reducing agent, a catalyst and an organic solvent, reacting, and post-treating to obtain the methyl pillar[5]arene daisy chain (MeP5C10-BzOH).

[0015] Preferably, the capping agent in step (3) is prepared by the following method:

[0016] (4-bromo-2,6-dimethylphenyl)methanol is mixed with a solvent, and then trimethylsilylene, a second catalyst and a catalyst promoter are added to react, and then a deprotecting agent is added, reacted again, and post-treated to obtain the capping agent.

[0017] In the preparation method of the capping agent, trimethylsilylene provides the alkyne protecting group.

[0018] Preferably, the solvent comprises triethylamine.

[0019] Preferably, the second catalyst comprises bis(triphenylphosphine)palladium dichloride.

[0020] Preferably, the catalyst promoter comprises cuprous iodide.

[0021] Preferably, the deprotecting agent comprises tetrabutylammonium fluoride.

[0022] Preferably, the molar ratio of the (4-bromo-2,6-dimethylphenyl)methanol, trimethylsilylene, the second catalyst, the catalyst aid and the deprotecting agent is 1:(1-1.3):(0.05-0.1):(0.1-0.2):(1-1.2), wherein 1-1.3 can be, for example, 1, 1.1, 1.2, 1.3, etc., (0.05-0.1) can be, for example, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, etc., 0.1-0.2 can be, for example, 0.1, 0.2, etc., and 1-1.2 can be, for example, 1, 1.1, 1.2, etc.

[0023] Preferably, the reaction temperature is 70-90°C, such as 70°C, 75°C, 80°C, 85°C, 90°C, etc., and the reaction time is 20-30 hours, such as 20 hours, 22 hours, 24 hours, 25 hours, 26 hours, 28 hours, 30 hours, etc.

[0024] Preferably, the reaction is carried out under the protection of an inert gas.

[0025] Preferably, the inert gas comprises nitrogen.

[0026] Preferably, the adding of the deprotecting agent is carried out at 20-40°C (eg, 20°C, 25°C, 30°C, 35°C, 40°C, etc.).

[0027] Preferably, the temperature of the secondary reaction is 20-40°C (eg, 20°C, 25°C, 30°C, 35°C, 40°C, etc.), and the time of the secondary reaction is 0.5-1.5 hours, eg, 0.5 hours, 1 hour, 1.5 hours, etc.

[0028] Preferably, the post-treatment includes drying and purification.

[0029] Preferably, the molar ratio of 4-(10-bromodecyloxy)anisole, p-dimethoxybenzene, paraformaldehyde and boron trifluoride ether in step (1) is 1:(6-8):(7-9):(8-10), wherein 6-8 can be, for example, 6, 7, 8, etc., 7-9 can be, for example, 7, 8, 9, etc., and 8-10 can be, for example, 8, 9, 10, etc.

[0030] Preferably, the organic solvent in step (1) comprises 1,2-dichloroethane.

[0031] Preferably, the reaction temperature in step (1) is 20-40°C (e.g., 20°C, 25°C, 30°C, 35°C, 40°C, etc.), and the reaction time is 10-20 minutes, e.g., 10 minutes, 15 minutes, 20 minutes, etc.

[0032] Preferably, the post-treatment in step (1) includes quenching, washing, and purification.

[0033] Preferably, the molar ratio of the monobromo-substituted methyl pillar[5]arene to sodium azide in step (2) is 1:(1-1.2), wherein 1-1.2 can be, for example, 1, 1.1, 1.2, etc.

[0034] Preferably, the organic solvent in step (2) comprises N,N-dimethylformamide.

[0035] Preferably, the reaction temperature in step (2) is 70-90°C, for example, 70°C, 75°C, 80°C, 85°C, 90°C, etc., and the reaction time is 10-20 hours, for example, 10 hours, 12 hours, 14 hours, 15 hours, 16 hours, 18 hours, 20 hours, etc.

[0036] Preferably, the reaction in step (2) is carried out under the protection of an inert gas.

[0037] Preferably, the inert gas comprises nitrogen.

[0038] Preferably, the post-treatment in step (2) includes drying and purification.

[0039] Preferably, the reducing agent in step (3) includes sodium ascorbate.

[0040] Preferably, the catalyst in step (3) comprises copper sulfate pentahydrate.

[0041] Preferably, the organic solvent in step (3) comprises dichloromethane.

[0042] Preferably, the molar ratio of the monoazido-substituted methoxy-pillar[5]arene (MeP5C10-N3), the capping agent, the reducing agent, and the catalyst in step (3) is 1:(0.9-1.1):(0.2-0.4):(0.05-0.1), wherein 0.9-1.1 can be, for example, 0.9, 1, 1.1, etc., 0.2-0.4 can be, for example, 0.2, 0.3, 0.4, etc., and 0.05-0.1 can be, for example, 0.05, 0.075, 0.1, etc.

[0043] Preferably, the reaction temperature in step (3) is 20-40°C, for example, 20°C, 25°C, 30°C, 35°C, 40°C, etc., and the reaction time is 90-100 hours, for example, 90 hours, 92 hours, 94 hours, 96 hours, 98 hours, 100 hours, etc.

[0044] Preferably, the reaction in step (3) is carried out under the protection of an inert gas.

[0045] Preferably, the inert gas comprises nitrogen.

[0046] Preferably, the post-treatment in step (3) includes drying and purification.

[0047] Preferably, the molecular weight of the polytetrahydrofuran is 500-5000 g / mol, for example, 500 g / mol, 1000 g / mol, 1500 g / mol, 2000 g / mol, 2500 g / mol, 3000 g / mol, 3500 g / mol, 4000 g / mol, 4500 g / mol, 5000 g / mol, etc., preferably 1000-3000 g / mol.

[0048] Preferably, the chain extender comprises 1,4-butanediol.

[0049] Preferably, the second cross-linking agent comprises trimethylolethane.

[0050] Preferably, the isocyanate comprises 3-isocyanatomethylene-3,5,5-trimethylcyclohexyl isocyanate.

[0051] Preferably, the catalyst comprises dibutyltin dilaurate.

[0052] Preferably, the organic solvent comprises tetrahydrofuran.

[0053] Preferably, based on the total mass of polytetrahydrofuran, chain extender, second cross-linking agent, isocyanate, catalyst and methyl pillar [5] aromatic hydrocarbon daisy chain as 100%, the amount of polytetrahydrofuran is 55%-75%, for example, 55%, 56%, 58%, 60%, 62%, 64%, 66%, 68%, 70%, 72%, 74%, 75%, etc., the amount of chain extender is 1%-2%, for example, 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, etc., and the amount of the second cross-linking agent is 1%- 2%, such as 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, etc., the amount of the isocyanate is 13%-20%, such as 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20%, etc., and the amount of the catalyst is 0.01%-0.05%, such as 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, etc.

[0054] Preferably, based on the total mass of polytetrahydrofuran, chain extender, second cross-linking agent, isocyanate, catalyst and methyl pillar[5]arene daisy chain as 100%, the amount of the methyl pillar[5]arene daisy chain is 5%-8%, for example, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, etc., so that the obtained pillar aromatic daisy chain polyurethane has a good toughening effect on the epoxy resin polymer.

[0055] Preferably, the reaction temperature is 50-70°C, such as 50°C, 55°C, 60°C, 65°C, 70°C, etc., and the reaction time is 2-4 hours, such as 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, etc.

[0056] Preferably, the epoxy resin comprises E51.

[0057] Preferably, the cross-linking agent comprises a polyetheramine.

[0058] Preferably, the molecular weight of the polyetheramine is 200-4000 g / mol, for example, 200 g / mol, 300 g / mol, 400 g / mol, 500 g / mol, 600 g / mol, 800 g / mol, 1000 g / mol, 1500 g / mol, 2000 g / mol, 2500 g / mol, 3000 g / mol, 3500 g / mol, 4000 g / mol, etc., preferably 400-600 g / mol.

[0059] Preferably, based on the total mass of the pillar aromatic daisy chain polyurethane, epoxy resin and cross-linking agent as 100%, the amount of the pillar aromatic daisy chain polyurethane is 0.3%-5%, for example, 0.3%, 0.4%, 0.5%, 1%, 2%, 2.5%, 3%, 4%, 5%, etc. By controlling the amount of the pillar aromatic daisy chain polyurethane within this range, the dynamic mechanical interlocking epoxy resin polymer can have both high tensile strength and high toughness.

[0060] Preferably, the mass ratio of the epoxy resin to the crosslinking agent is (1.5-2.5):1, wherein 1.5-2.5 can be, for example, 1.5, 1.8, 2, 2.2, 2.3, 2.5, etc.

[0061] In a second aspect, the present invention provides a method for preparing the mechanically interlocking epoxy resin polymer according to the first aspect, the preparation method comprising the following steps:

[0062] The pillar aromatic daisy chain polyurethane, epoxy resin, crosslinking agent and organic solvent are mixed and cured to obtain the mechanical interlocking epoxy resin polymer.

[0063] Preferably, the mixing further comprises a step of ultrasonic treatment.

[0064] Preferably, the ultrasonic treatment time is 20-40 minutes, for example, 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, etc.

[0065] Preferably, the curing temperature is 60-120°C, for example, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, etc., and the curing time is 12-72 hours, for example, 12 hours, 24 hours, 36 hours, 48 hours, 60 hours, 72 hours, etc.

[0066] In a third aspect, the present invention provides a use of the mechanically interlocking epoxy resin polymer as described in the first aspect in the preparation of a high-strength and high-toughness polymer.

[0067] Compared with the prior art, the present invention has the following beneficial effects:

[0068] In the present invention, pillar aromatic hydrocarbon daisy chain polyurethane, epoxy resin, and crosslinking agent are subjected to ring-opening polymerization to form a mechanically interlocked polymer containing a daisy chain. The crosslinking agent crosslinks the polymer containing the daisy chain into a network. The prepared mechanically interlocked epoxy resin polymer has dynamic properties, which mainly come from the host-guest recognition effect of pillar aromatic hydrocarbon and triazole. It can improve the mechanical properties and energy dissipation of traditional epoxy resins, enable the epoxy resin to withstand greater stress, enhance its toughness, and promote maximum elongation and ductility without sacrificing the mechanical strength of the polymer. BRIEF DESCRIPTION OF THE DRAWINGS

[0069] Figure 1 Schematic diagram of the synthesis route of the methyl pillar [5] aromatic hydrocarbon daisy chain provided in Preparation Example 2 of the present invention.

[0070] Figure 2 The nuclear magnetic hydrogen spectrum of the methyl column [5] aromatic hydrocarbon daisy chain provided in Preparation Example 2 of the present invention ( 1 H NMR).

[0071] Figure 3 The infrared absorption spectrum (FTIR) graphs of the epoxy resin polymers provided in Example 1, Example 2, Example 3, and Comparative Example 1 of the present invention are shown.

[0072] Figure 4 Differential Scanning Calorimetry (DSC) diagrams of the epoxy resin polymers provided in Example 1, Example 2, Example 3, and Comparative Example 1 of the present invention.

[0073] Figure 5 Thermogravimetric analysis diagrams of epoxy resin polymers provided in Example 1, Example 2, Example 3, and Comparative Example 1 of the present invention.

[0074] Figure 6 This is a stress-strain curve diagram of the epoxy resin polymer provided in Example 1, Example 2, Example 3, and Comparative Example 1 of the present invention.

[0075] Figure 7 This is a stress-strain curve diagram of the epoxy resin polymer provided in Example 4, Example 5, Example 6, and Comparative Example 2 of the present invention. DETAILED DESCRIPTION

[0076] The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0077] Preparation Example 1

[0078] In this preparation example, a capping agent is provided, the structure of which is shown in the following formula A. The preparation method includes the following steps:

[0079]

[0080] Formula A

[0081] (4-Bromo-2,6-dimethylphenyl)methanol (0.4 g, 2 mmol), trimethylsilylene (0.23 g, 2.4 mmol), bis(triphenylphosphine)palladium dichloride (37.5 mg, 0.15 mmol), and cuprous iodide (255 mg, 0.3 mmol) were added to 80 mL of triethylamine and stirred at 80°C under nitrogen for 24 hours. After the reaction was complete, tetrabutylammonium fluoride (0.55 g, 2.2 mmol) was added at room temperature and stirred for 1 hour. After the reaction, the layers were separated, and the organic phase was dried, filtered, and dried to dryness to obtain a black crude product. The crude product was separated by column chromatography (eluent: petroleum ether / dichloromethane = 1:1, v / v) to obtain a light yellow solid powder capping agent (0.19 g, 61% yield).

[0082] The characterization data of the capping agent are as follows:

[0083] 1 H NMR (600 MHz, Chloroform-d) δ 7.19 (s, 2H), 4.73 (d, J = 5.0 Hz, 2H), 3.03 (s, 1H), 2.41 (s, 6H).

[0084] Preparation Example 2

[0085] In this preparation example, a methyl pillar[5]arene daisy chain is provided, and the preparation method includes the following steps:

[0086] (1) Synthesis of monobromo-substituted methyl pillar[5]arene MeP5C10-Br having the structure shown in Formula I below.

[0087]

[0088] Formula I

[0089] p-Dimethoxybenzene (9.8 g, 70 mmol) and 4-(10-bromodecanyloxy)anisole (1.53 g, 10 mmol) were added to 100 mL of 1,2-dichloroethane, and paraformaldehyde (1.2 g, 80 mmol) and boron trifluoride etherate (9.1 mL, 80 mmol) were added. The mixture was stirred at room temperature for 15 minutes. After the raw materials disappeared completely, saturated sodium bicarbonate solution was added to stop the reaction. The mixture was allowed to stand and separated to obtain an organic phase. The organic phase was washed twice with saturated sodium bicarbonate solution and concentrated under reduced pressure to obtain a crude product. The crude product was purified by flash column chromatography (volume ratio of eluent petroleum ether / dichloromethane = 1:1) to obtain compound monobromosubstituted methyl column [5]arene (0.72 g, yield 31%), which was a white powder and was recorded as compound MeP5C10-Br.

[0090] MeP5C10-Br characterization data are as follows:

[0091] MeP5C10-Br. 1 H NMR (400 MHz, CDCl3, 298 K) δ ppm 7.06 – 6.68 (m, 10H), 3.95 (s, 2H), 3.89 – 3.62 (m, 37H), 1.86 (t, J = 7.0 Hz, 2H), 1.66 – 1.19 (m,6H), 1.08 (p, J = 7.4 Hz, 2H), 0.77 – 0.49 (m, 2H), -0.23 (s, 2H), -0.51 (s,2H), -0.89 (s, 2H).

[0092] (2) Synthesis of monoazido-substituted methoxy-pillar[5]arene MeP5C10-N3 having the structure shown in Formula II

[0093]

[0094] Formula II

[0095] Monobromosubstituted methyl pillar[5]arene MeP5C10-Br (0.67 g, 0.7 mmol) and sodium azide (54 mg, 0.84 mmol) were added to 50 mL of N,N-dimethylformamide and stirred at 80°C for 12 hours. After the raw materials reacted completely, the layers were separated, and the organic phase was dried, filtered, and dried to obtain a crude product. The crude product was separated by column chromatography (eluent: petroleum ether / ethyl acetate = 20:1, v / v) to obtain a light yellow solid powder of monoazidosubstituted methoxy pillar[5]arene, recorded as MeP5C10-N3 (0.6 g, yield 87%).

[0096] MeP5C10-N3 characterization data are as follows:

[0097] Compound MeP5C10-N3. 1H NMR (400 MHz, CDCl3, 298 K) δ ppm 6.91 – 6.76 (m,10H), 3.91 (t, J = 6.4 Hz, 2H), 3.83 – 3.63 (m, 37H), 2.15 (s, 2H), 1.81 (p,J = 6.9 Hz, 2H), 1.50 (t, J = 7.2 Hz, 2H), 1.38 – 1.26 (m, 2H), 1.12 (q, J =7.5 Hz, 2H), 0.79 (t, J = 7.7 Hz, 2H), 0.38 – 0.19 (m, 2H), 0.15 (s, 4H), -0.08 (s, 2H).

[0098] (3) Synthesis of a methyl-pillar[5]arene daisy chain MeP5C10-BzOH having the structure shown in Formula III

[0099]

[0100] Formula III

[0101] Monoazido-substituted methoxy column [5] arene MeP5C10-N3 (0.45 g, 0.5 mmol), the capping agent provided in Preparation Example 1 (75 mg, 0.55 mmol), sodium ascorbate (20 mg, 0.1 mmol) and copper sulfate pentahydrate (6 mg, 0.025 mmol) were added to 5 mL of dichloromethane and stirred at room temperature for 96 hours under nitrogen protection. The layers were separated, and the organic phase was dried, filtered, and dried to obtain an orange-yellow crude product. The crude product was separated by column chromatography (eluent: dichloromethane / ethyl acetate = 20:1, v / v) to obtain a light yellow solid powder methyl column [5] arene daisy chain, recorded as MeP5C10-BzOH (0.95 g, yield 90%).

[0102] The characterization data of MeP5C10-BzOH are as follows:

[0103] Compound MeP5C10-BzOH. 1H NMR (400 MHz, CDCl3, 298 K) δ ppm 7.64 (s, 2H), 6.93 (s, 1H), 6.85 (dt, J = 3.7, 1.7 Hz, 10H), 4.80 (s, 2H), 4.03 (t, J = 5.6Hz, 2H), 3.81 – 3.70 (m, 30H), 3.64 (s, 6H), 3.62 (s, 3H), 3.58 (s, 3H), 3.54(s, 3H), 2.21 (t, J = 7.6 Hz, 2H), 2.01 (d, J = 6.5 Hz, 2H), 1.85 – 1.76 (m,2H), 1.15 – 1.06 (m, 4H), 0.66 (s, 2H), -0.15 (s, 2H), -0.75 (s, 2H).

[0104] The schematic diagram of the synthesis route of the methyl pillar [5] aromatic daisy chain provided in this preparation example is as follows Figure 1 shown.

[0105] The hydrogen nuclear magnetic spectrum of the methyl column [5] aromatic daisy chain provided in this preparation example is ( 1 H NMR) Figure 2 As shown in the figure, it can be seen that there are negatively shifted H on the pillararenes. This is because the pillararenes form an interpenetrating dimer structure, namely a daisy chain, and H penetrates into the cavity of the adjacent pillararenes.

[0106] Preparation Example 3

[0107] In this preparation example, a pillar aromatic daisy chain polyurethane is provided, and the preparation method comprises the following steps:

[0108] 1.8 g of polytetrahydrofuran (number average molecular weight Mn = 2000 g / mol), 40 mg of 1,4-butanediol, 46 mg of trimethylolethane, 444 mg of 3-isocyanate methylene-3,5,5-trimethylcyclohexyl isocyanate, 500 μL of dibutyltin dilaurate and (194 mg) of the methyl columnar [5] aromatic hydrocarbon daisy chain MeP5C10-BzOH provided in Preparation Example 2 were added to 20 mL of tetrahydrofuran and reacted at 60° C. After 3 hours, the mixture was poured into a polytetrafluoroethylene mold and then dried at 60° C. to obtain a white transparent columnar aromatic hydrocarbon daisy chain polyurethane.

[0109] Example 1

[0110] In this embodiment, a mechanically interlocking epoxy resin polymer is provided, and a preparation method thereof comprises the following steps:

[0111] 4.0 g of epoxy resin E51, 2.0 g of polyetheramine (Mn = 400 g / mol), 0.02 g of pillar aromatic daisy chain polyurethane (provided in Preparation Example 3) and 20 mL of dichloromethane were mixed in a 100 mL round-bottom flask, ultrasonically treated for 30 minutes, and then mixed evenly by magnetic stirring. The mixture was poured into a polytetrafluoroethylene mold and cured at 90°C for 12 hours to obtain a white mechanically interlocking epoxy resin polymer, which was recorded as D400-Pdaisy chain-1.

[0112] Comparative Example 1

[0113] The only difference between this comparative example and Example 1 is that the pillar aromatic daisy chain polyurethane is not added, and the rest are the same. The obtained epoxy resin polymer is recorded as D400.

[0114] Example 2

[0115] The only difference between this example and Example 1 is that the amount of pillar aromatic daisy chain polyurethane used is 0.04 g, and all other aspects are the same. The obtained mechanically interlocked epoxy resin polymer is recorded as D400-Pdaisy chain-2.

[0116] Example 3

[0117] The only difference between this example and Example 1 is that the amount of pillar aromatic daisy chain polyurethane used is 0.20 g, and all other aspects are the same. The obtained mechanically interlocked epoxy resin polymer is recorded as D400-Pdaisy chain-3.

[0118] Example 4

[0119] In this embodiment, a mechanically interlocking epoxy resin polymer is provided, and a preparation method thereof comprises the following steps:

[0120] 4.0 g of epoxy resin E51, 2.4 g of polyetheramine (Mn = 600 g / mol), 0.02 g of pillararomatic daisy chain polyurethane (from Preparation Example 3), and 20 mL of dichloromethane were mixed in a 100 mL round-bottom flask. Ultrasonic treatment was performed for 30 minutes, followed by magnetic stirring to mix thoroughly. The mixture was then poured into a polytetrafluoroethylene mold and cured at 90°C for 12 hours to obtain a white, mechanically interlocked epoxy resin polymer, designated ED600-Pdaisy Chain-1.

[0121] Comparative Example 2

[0122] The only difference between this comparative example and Example 4 is that the pillar aromatic daisy chain polyurethane is not added, and the rest are the same. The obtained epoxy resin polymer is recorded as ED600.

[0123] Example 5

[0124] The only difference between this example and Example 4 is that the amount of pillar aromatic daisy chain polyurethane used is 0.04 g, and all other aspects are the same. The obtained mechanically interlocked epoxy resin polymer is recorded as ED600-Pdaisy chain-2.

[0125] Example 6

[0126] The only difference between this example and Example 4 is that the amount of pillar aromatic daisy chain polyurethane used is 0.20 g, and all other aspects are the same. The obtained mechanically interlocked epoxy resin polymer is recorded as ED600-Pdaisy chain-3.

[0127] The infrared absorption spectrum (FTIR) of the epoxy resin polymer provided in Example 1, Example 2, Example 3 and Comparative Example 1 of the present invention is shown in FIG. Figure 3 shown.

[0128] The differential scanning calorimetry (DSC) diagrams of the epoxy resin polymers provided in Example 1, Example 2, Example 3, and Comparative Example 1 of the present invention are as follows: Figure 4 As shown, it can be seen that after the addition of pillar aromatic daisy chain polyurethane, the Tg of the polymer network decreases with the increase of the proportion of pillar aromatic daisy chain polyurethane, which also shows that the elasticity of the epoxy resin polymer continues to increase.

[0129] The thermogravimetric analysis diagrams of the epoxy resin polymers provided in Example 1, Example 2, Example 3 and Comparative Example 1 of the present invention are as follows: Figure 5 As shown, it can be seen that after adding pillar aromatic daisy chain polyurethane, the entire polymer network can still maintain good thermal stability.

[0130] The epoxy resin polymers provided in the examples and comparative examples of the present invention were tested for stress-strain, fracture strength, and toughness using an Instron 34SC-1 at a tensile speed of 5 mm / min.

[0131] The stress-strain curves of the epoxy resin polymers provided in Example 1, Example 2, Example 3 and Comparative Example 1 of the present invention are shown in FIG. Figure 6 As shown, it can be seen that after the addition of columnar aromatic hydrocarbon daisy chain polyurethane, the tensile strength of the polymer network will decrease slightly, and the elongation will increase, indicating that the addition of columnar aromatic hydrocarbon daisy chain polyurethane gives the entire epoxy polymer dynamics and toughness, and the toughening effect of the epoxy resin polymer prepared in Example 2 is the best.

[0132] The test results of the fracture strength and fracture toughness of the epoxy resin polymers provided in Examples 1-3 of the present invention and Comparative Example 1 are shown in Table 1 below:

[0133] Table 1

[0134]

[0135] It can also be seen from Table 1 that, compared with Comparative Example 1, the toughness of the epoxy resin polymers provided in Examples 1-3 of the present invention is improved.

[0136] The stress-strain curves of the epoxy resin polymers provided in Example 4, Example 5, Example 6, and Comparative Example 2 of the present invention are shown in FIG. Figure 7 As shown, it can be seen that the addition of pillar aromatic daisy chain polyurethane gives the entire epoxy polymer good ductility and toughness, and the epoxy resin polymer prepared in Example 5 has the best toughening effect.

[0137] The applicant states that while the above-described embodiments illustrate the mechanically interlocking epoxy resin polymer, its preparation method, and its application, the present invention is not limited to these embodiments. This does not necessarily mean that the present invention must rely on these embodiments in order to be implemented. Those skilled in the art will understand that any improvements to the present invention, equivalent substitutions for the raw materials used, additions of auxiliary components, and selection of specific methods, etc., fall within the scope of protection and disclosure of the present invention.

Claims

1. A mechanically interlocking epoxy resin polymer, characterized in that The raw materials for preparing the mechanical interlocking epoxy resin polymer include pillar aromatic hydrocarbon daisy chain polyurethane, epoxy resin and cross-linking agent; The pillar aromatic daisy chain polyurethane is prepared by the following method: Adding polytetrahydrofuran, a chain extender, a second cross-linking agent, an isocyanate, a catalyst and a methyl pillar[5]arene daisy chain into an organic solvent, reacting the mixture to obtain the pillararene daisy chain polyurethane; The second cross-linking agent includes trimethylolethane; The methyl pillar [5] aromatic daisy chain is prepared by the following method: (1) p-Dimethoxybenzene, 4-(10-bromodecanyloxy)anisole and an organic solvent are mixed, and then paraformaldehyde and boron trifluoride ether are added, reacted, and post-treated to obtain monobromo-substituted methyl pillar[5]arene; (2) mixing monobromo-substituted methyl pillar[5]arene, sodium azide and an organic solvent, reacting, and post-treating to obtain monoazido-substituted methoxy pillar[5]arene; (3) mixing the monoazido-substituted methoxy pillar[5]arene, a capping agent, a reducing agent, a catalyst and an organic solvent, reacting, and post-treating to obtain the methyl pillar[5]arene daisy chain; The capping agent in step (3) is prepared by the following method: Mixing (4-bromo-2,6-dimethylphenyl)methanol with a solvent, then adding trimethylsilylene, a second catalyst, and a catalyst promoter, reacting, then adding a deprotecting agent, reacting again, and post-treating to obtain the end-capping agent; The cross-linking agent includes polyetheramine.

2. The mechanically interlocking epoxy resin polymer according to claim 1, wherein During the preparation of the capping agent: The solvent includes triethylamine; The second catalyst comprises bis(triphenylphosphine)palladium dichloride; The catalyst promoter includes cuprous iodide; The deprotecting agent includes tetrabutylammonium fluoride; The molar ratio of (4-bromo-2,6-dimethylphenyl)methanol, trimethylsilylene, the second catalyst, the catalyst promoter and the deprotecting agent is 1:(1-1.3):(0.05-0.1):(0.1-0.2):(1-1.2); The reaction temperature is 70-90°C and the reaction time is 20-30 hours; The reaction is carried out under the protection of inert gas; The adding of the deprotecting agent is carried out at 20-40° C.; The temperature of the secondary reaction is 20-40°C, and the time of the secondary reaction is 0.5-1.5 hours; The post-processing includes drying and purification.

3. The mechanically interlocking epoxy resin polymer according to claim 1, wherein The molar ratio of 4-(10-bromodecyloxy)anisole, p-dimethoxybenzene, paraformaldehyde and boron trifluoride ether in step (1) is 1:(6-8):(7-9):(8-10); The organic solvent in step (1) includes 1,2-dichloroethane; The reaction temperature in step (1) is 20-40°C and the reaction time is 10-20 minutes; The post-treatment in step (1) includes quenching, washing, and purification.

4. The mechanically interlocking epoxy resin polymer according to claim 1, wherein The molar ratio of the monobromo-substituted methyl pillar [5]arene to sodium azide in step (2) is 1:(1.0-1.2); The organic solvent in step (2) includes N,N-dimethylformamide; The reaction temperature in step (2) is 70-90°C and the reaction time is 10-20 hours; The reaction in step (2) is carried out under the protection of an inert gas; The post-processing in step (2) includes drying and purification.

5. The mechanically interlocking epoxy resin polymer according to claim 1, wherein The reducing agent in step (3) includes sodium ascorbate; The catalyst in step (3) includes copper sulfate pentahydrate; The organic solvent in step (3) includes dichloromethane; In step (3), the molar ratio of the monoazido-substituted methoxy-pillar[5]arene, the end-capping agent, the reducing agent, and the catalyst is 1:(0.9-1.1):(0.2-0.4):(0.05-0.1); The reaction temperature in step (3) is 20-40°C and the reaction time is 90-100 hours; The reaction in step (3) is carried out under the protection of an inert gas; The post-processing in step (3) includes drying and purification.

6. The mechanically interlocking epoxy resin polymer according to claim 1, wherein The molecular weight of the polytetrahydrofuran is 500-5000 g / mol; The chain extender includes 1,4-butanediol; The isocyanate includes 3-isocyanatomethylene-3,5,5-trimethylcyclohexyl isocyanate; The catalyst includes dibutyltin dilaurate; The organic solvent includes tetrahydrofuran; Based on the total mass of polytetrahydrofuran, chain extender, second cross-linking agent, isocyanate, catalyst and methyl pillar[5]arene daisy chain as 100%, the amount of polytetrahydrofuran is 55%-75%, the amount of chain extender is 1%-2%, the amount of second cross-linking agent is 1%-2%, the amount of isocyanate is 13%-20%, and the amount of catalyst is 0.01%-0.05%; Based on the total mass of polytetrahydrofuran, chain extender, second cross-linking agent, isocyanate, catalyst and methyl pillar[5]arene daisy chain as 100%, the amount of the methyl pillar[5]arene daisy chain is 5%-8%; During the preparation of the pillar aromatic daisy chain polyurethane, the reaction temperature is 50-70° C. and the reaction time is 2-4 hours.

7. The mechanically interlocking epoxy resin polymer according to claim 1, wherein: The epoxy resin includes E51; The molecular weight of the polyetheramine is 200-4000 g / mol; Based on the total mass of the pillar aromatic hydrocarbon daisy chain polyurethane, the epoxy resin and the crosslinking agent as 100%, the amount of the pillar aromatic hydrocarbon daisy chain polyurethane is 0.3%-5%; The mass ratio of the epoxy resin to the crosslinking agent is (1.5-2.5):

1.

8. A method for preparing a mechanically interlocking epoxy resin polymer according to any one of claims 1 to 7, characterized in that: The preparation method comprises the following steps: Mixing pillar aromatic daisy chain polyurethane, epoxy resin, crosslinking agent and organic solvent, and curing to obtain the mechanically interlocked epoxy resin polymer; The mixing further comprises the step of ultrasonic treatment; The ultrasonic treatment time is 20-40 minutes; The curing temperature is 60-120° C., and the curing time is 12-72 hours.

9. Use of the mechanically interlocking epoxy resin polymer according to any one of claims 1 to 7 in the preparation of high-strength and high-toughness polymers.

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